Triazine derivatives



Patented Mar. 2, 1943 OFFICE TRIAZlNE DERIVATIVES Gaetano F. DAlelio, Pittsfield, Mass, assignor to General Electric Company, a corporation of New York No Drawing. Application December 19, 1941,

7 Serial No. 423,691

15 Claims.

In the above formula n represents an integer and is at least 1 and not more than 2, Z represents a member of the class consisting of oxygen and sulfur, Y represents a divalent canbocyclic radical, and R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and substituted hydrocarbon radicals, more particularly halohydrocarbon radicals. Since 11. represents an integer which is 1 or 2, it will be I seen that the linkage of the hydroxycarbocycliccarbamyl-alkyl or hydroxycarbocyclic-thiocarbamyl-alkyl grouping to the sulfur atom in all cases will be alpha or beta to the hydroxycarbocyclic-carbamyl or -thiocarbamyl grouping. It also will be observed that linkage of thetriazinyl grouping to the sulfur atom is through a carbon atom.

illustrative examples of, radicals that R in the above formula may represent are: aliphatic (e. g., methyl, ethyl, propyl, isopropyl; allyl, butyl, secondary butyl, isobutyl, butenyl, amyl, isoamyl', hexyl, etc.) including cycloaliphatic (e. g., cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, etc.) aryl (e. g., phenyl, diphenyl or xenyl, naphthyl, etc.); aliphatic-substituted aryl (e. g., tolyl, xylyl, ethylphenyl, propylphenyl, isopropylphenyl, allylphenyl, 2-butenylphenyl, tertiary-butylphenyl, etc); aryl-substituted aliphatic (e. g., benzyl, phenylethyl, phenylisopropyl, cinnamyl, etc.) and their homolgues, as well as those groups with one or more of their hydrogen atoms substituted by, for example, a halogen. Specific examples of halogeno-substituted hydrocarbon radicals are chloromethyl, chloroethyl, chlorophenyl, dichlorophenyl, chlorocyclohexyl, ethyl chlorophenyl, phenyl' chloroethyl, bromoethyl, bromopropyl, bromotolyl, etc. Preferably R in Formula I is hydrogen. However, there also may be produced in accordance with the present invention compounds such, for instance, as those represented by the general formulas:

where 12, Z, Y and R have the same meanings as above given with reference to Formula I.

Illustrative examples of divalent carbocyclic radicals which Y in Formulas I, II and III may represent are: divalent, aromatic, e. g., phenylene, xenylene, naphthylene, etc.; divalent aliphaticsubstituted aromatic e. g., 2,5-toly1ene, para- (2,3-xylylene), etc.; divalent cycloaliphatic, e. g.,'

cyclopentylene, cyclohexylene, cyclopentenylene, cyclohexenylene, cycloheptylene, etc.; and their homologues, as well as those divalent carbocyclic radicals with one or more of their hydrogen atoms replaced by a substituent, e. g., halogeno, amino, acetyl, acetoxy, carboalkoxy, alkoxy, aryloxy, sulfamyl, alkyl, alkenyl, a hydroxy group or groups. in addition to the single OH group shown in the above formulas, etc. Specific examples of substituted divalent carbocyclic radicals are chlorophenylene, bromophenylene, chloronaphthylene, bromonaphthylene, bromo 2,5-tolylene, chlorocyclopentylene, chlorocyclopentenylene, carbomethoxyphenylene, ethoxvphenylene, acetophenylene, acetoxyphenylene, bromocyclopentylene, aminophenylene, phenoxyphenylene. sulfamylphenylene, methylphenylene (tolylene), allylphenylene, etc. Preferably Y is phenylene or methylphenylene.

The new compounds of this invention may be used, for example, as pharmaceuticals, plasticizers and as intermediates in the preparation of derivatives thereof such as hydrazo, hydrazino, carbazido, semicarbazido, ureido, carbamyl, acyl, amidine, methylol, etc., derivatives of the individual compound embraced by Formula I. These new organic sulfides are especially valuable in the preparation of synthetic resinous compositions. Thus, they may be condensed with, for instance, aldehydes, including polymeric aldehydes and aldehyde-addition products, to yield condensation products of particular utility in the plastics and coating arts. Such condensation products are more fully described and are specifically claimed in my copending application Serial No. 424,330, filed December 24, 1941, and assigned to the same assignee as the present invention. These new organic sulfides also may be compounded with rubber, both natural and synthetic, to modify the properties of the rubber.

Various methods may be employed to produce the chemical compounds of this invention. I preier to prepare them by a process which comprises eifecting reaction between a diamino U-NHRm mercapto symmetrical triazine (s-triazine) and a hydroxycarbocyclic-carbamyl-alkyl halide (or a hydroxycarbocyclic-thiocarbamyl-alkyl in the presence of a hydrohalide acceptor, e. g., an alkali-metal hydroxide. When the starting components, proportions thereof and reaction conditions are such that the hydrogen atom of the -OH group of the hydroxycarbocyclic compound is replaced by the residue of the hydrohalide acceptor, e. g., by an alkali metal, the hydroxy compound desired as a final product is obtained by treating this intermediate product with hydrochloric, hydrobromic, sulfuric or other suitable organic or inorganic acid in an amount justsufiicient to form the desired hydroxy derivative.

Illustrative examples of mercapto diamino striazines that may be used, depending upon the particular end-product desired, are:

2-mercapto 4-dichloroanllino fi-chloroethylamino s-triazine z-mercapto 4-amino fi-bromoethylamino s-triazine 2-mercapto 4-amino fi-methylamino s-triazine 2-mercapto 4 -aminoanilino G-ethylphenylamino s-triazine 2-mercapto 4-amino 6-benzylamino s-triazine Z-mercapto 4,6-di-(methylamino) s-triazine Z-mercapto 4,6-di-(anilino) s-triazine 2-mercapto 4-amino 6-ethylamino s-triazine 2-mercapto 4,6-di-(propylamino) s-triazine z-mercapto 4-allylamino fi-butylamino s-triazine halide) 2-mercapto 4-isobutylamino S-cyclopentylamino s-triazine 2-mercapto 4-(3'-butenylamino) amino s-triazine Z-mercapto 4-pentylamino G-cyclohexylamino striazine 2-mercapto 4-n-hexylamino fi-xenylamino 6- naphthylamino s-triazine Illustrative examples of. hydroxycarbocyclic carbamyl-alkyl halides and hydroxycarbocyclicthiocarbamyl-alkyl halides that may be ememployed, depending upon the particular'endproduct sought, are:

6-isopropy1- alpha- Para-hydroxyphenyl (chloroethyl) carbamyl chloro Alpha-[4-hydroxy 2-chloro cyclopentyl- (xenyl) carbamyl] alpha-chloroxylyl beta-chloro ethane Alpha-(para hydroxyphenyl carbamyl) alphaiodo omega-chloro pentane Hydroxycyclohexenyl (phenylisopropyl) carbamyl chlorocyclopentenyl chloro methane Alpha- [para hydroxyxenyl (isobutylphenyl) carbamyl] beta-naphthyi-beta-bromo ethane Alpha-[para-hydroxy chloro phenyl-(isopentyl) thiocarbamyll alpha-ethyl alpha tolyl betaphenyl beta-bromo propane Various hydrohalide acceptors may' be employed. I prefer to use a hydrohalide acceptor that will react with the mercapto triazine to form a water-soluble salt. Examples of such acceptors are the alkali-metal hydroxides, e. g., sodium hydroxide, potassium hydroxide, etc. Additional examples of hydrohalide acceptors that may be used are other inorganic bases, e. g., calcium hydroxide, barium hydroxide, ammonium hydroxide, etc.; carbonates of inorganic Y bases, including the carbonates of alkali metals;

organic amines such as tertiary amines, e. g., trimethyl amine, trlethyl amine, tributyl amine, pyridine, dimethyl aniline,.quinoline, etc.; quaternary ammonium bases, e. g., tetramethyl ammonium hydroxide, etc. and the like.

The reaction between the mercapto diamino s-triazine and the hydroxycarbocyclic-carbamyl alkyl halide (or hydroxycarbocyclic-thiocarbamyl-alkyl halide) may be carried out in any suitable manner, but preferably is effected in the presence of a suitable solvent or mixture of bocyclic-thiocarbamyl may be used, depending upon the particular endsolvents. Although various solvents and solvent mixtures may be employed, for economic reasons and because of their eminent suitability I prefer to use water or a mixture of water and alcohol. The reaction may be carried out under a variety of temperature and pressure con: ditions, for instance at normal, sub-normal or at elevated temperatures and at atmospheric, sub-atmospheric or super-atmospheric pressures. However, normal pressures and temperatures are preferred for convenience.

The new chemical compounds of this invention also may be prepared by a process which comprises effecting reaction between a halogenated diamino s-triazine and a hydroxycarbocyclio-carbamyl mercapto alkane (or a hydroxycarbocyclic-thlocarbamyl mercapto alkane) in the presence of a hydrohalide acceptor. This reaction preferably is carried out in the presence of an anhydrous solvent. An anhydrous solvent, e. g., alcohol, is desirable because one of the reactants, namely, the halogenated diamino s-triazine is hydrolyzable. The other conditions for preparing the compounds of the invention may be the same as described above with reference to the first-mentioned method of preparation.

Illustrative examples of halogenated diamino s-triazines that may be used, depending on the end-product desired, are:

2-.chloro 4,6-diamlno s-triazine Z-bromo 4,6-diamino s-triazine 2-iodo 4,6-diamino s-trlazine 2-chloro 4,6-di-(methylamino) s-triazine 2-chloro 4,6-di-(anilino) s-triazine 2-bromo -amino S-ethylamino s-triazine 2-chloro 4,6-di-(propylamino) s-triazine 2-bromo 4-allylamino G-butylamino s-triazine 2-chloro -isobutylamino fi-cyclopenty'lamino s-triazine 2-ch1oro 4-(3-butenylamino) fi-isopropylamino s-triazine 2-chloro 4-amylamino G-cyclohexylamino s-triazine 2'-chloro 4-n-hexylamino 6-xenylamino s-triazine 2-bromo 4-cyclohexenylamino G-naphthy'lamino s-triazine 2-chloro d-chlorocyclopentylamino s-triazine 2-chloro -bromotoluldo 6-benzylamino s-triazine 2-chloro -phenylchloroethylamino fi-phenethylamino s-triazine 2-chloro -aminoanilino fi-ethylanilino s-triazine 2-chloro -chlorocycloheptylamino 6-isopropy1- phenylamino s-triazine 2-chloro 4-isopropylanilino fi-phenylpropylamino s-triazine Q 2-bromo 4-dichloroanilin'o 6-chloroethylamino s-triazine 2-iodo 4-amino 6-bromoethylamino s-triazine 6-toluido Illustrative examples of hydroxycarbocycliccarbamyl mercapto alkanes and of hydroxycarmercapto alkanes that product desired, are:

Para-hydroxyphenyl-carbamyl mercapto methane Alpha (para hydroxyphenyl carbamyl) mercapto ethane Alpha-(meta-hydroxyphenyl-carbamyl)' alphamercapto ethane beta- Alpha-(para-hydroxyphenyl-thiocarbamyl) alpha-mercapto pentane Ortho-hydroxyphenyl-(methyl) -carbamyl mercapto methane Alpha- (d-hydroxynaphthyll -carbamyl) betamercapto butene Alpha-(para-hydroxy chloro phenyl-carbamyl) alpha-ethyl beta-phenyl beta-mercapto ethane Hydroxytolyl carbamyl cyclopentyl mercapto methane Hydroxytolyl-(butyl) -carbamyl mercapto methane Para-hydroxyphenyl- (cyclopentyl) -thiocarbamyl mercapto methane Para hydroxyphenyl mercapto methane -hydroxycyclohexyl -(phenyl) carbamyl mercapto methane 3-hydroxycyclopentyl-carbamyl tolyl mercapto methane Alpha [para hydroxy chlorophenyl (bromophenyD-thiocarbamyl] alpha-chlorocyclohexenyl beta-mercapto ethane Alpha- [hydroxy broaro cyclopentyl-(xenyl) -carbamyll alpha-(chloroxylyl) beta-mercapto ethane Alpha-(para-hydroxyphenyl-carbamyl) mercapto omega-chloro pentane Hydroxycyclohexenyl (phenyllsopropyl) carbamyl cyclopentenyl mercapto methane Alpha [para hydroxyxenyl -(buty1phenyl) carbamyll beta-naphthyl beta-mercapto ethane Alpha- [para-hydroxy'chloro phenyl- (isopentyl) thiocarbamyll alpha-ethyl alpha-tolyl betaphenyl beta-mercapto ethane (chloroethyl) carbamyl alpha- In order that those skilled in the art better may understand how the present invention may be carried into effect, the following illustrative examples are given. All parts are by weight.

Example 1 This example illustrates the preparation of diamino s-trlazinyl para-hydroxyphenyl-carbamyl methyl'sulflde.

The mercapto diamino s-triazine was added to a solution of the sodium hydroxide dissolved in 250 parts water. Stirring was continued until a clear solution resul d. The para-(chloroacetamido) phenol (para-hydroxyphenyl-carbamyl chloro methane) was now added and the mixture was stirred for 1 hour. An additional ten grams or sodium hydroxide was added to the reaction mass in order more quickly to dissolve the mercapto compound. The undissolved solid disappeared almost immediately, indicating complete conversion to the phenolate form. The solution was filtered and the filtered solution then was stirred for 30 minutes. An acid, specifically hydrochloric acid, was added to the clear solution in an amount just sufilcient to make the solution neutral to litmus.

approximately 38% HCl was sufllcient to neutration and washed free residue was dried at 70 C. for

One hundred and three (103) parts of hydrochloric acid solution containing yield of dried product was approximately 92% of the theoretical amount obtainable.

The following equations represent the reactions which are believed to take place:

NH, NE:

IV-a

IV-b

O NH] N N g H +Ci-OHr -NH ONa HiN-C -SNa N IV-c o I elm-( t d-s-oHrg-NnO-oNHNam l-v w IV d NH:

The para-(chloroacetamido) phenol used as a reactant in preparing the compound of this example is a very powerful vesicant. In marked contrast the diamino s-triazinyl para-hydroxyphenyl-carbamyl-methyl sulfide has little or no irritating characteristics.

The diamino s-triazinyl para-hydroxyphenylcarbamyl-methyl sulfide can be obtained directly, that is, without the acidification step, by using only sufiicient sodium hydroxide to form the sodium salt of the mercapto diamino s-triazine as an intermediate product.

Example 2 4,6-di-(methylamino) s-triazinyl-2 para-hydroxyphenyl-carbamyl-methyl sulfide, which also may be named 2,6-di-(methylamino) s-triazinyl- 4 para-hydroxyphenyl-carbamyl-methyl sulfide or 2,4-di-(methylamino) s-triazinyl-6 para-hydroxyphenyl-carbamyl-methyl sulfide, is prepared in essentially the same manner as described under Example 1 with the exception that, instead or mercapto diamino s-triazine, an equivalent amount of 2-mercapto 4,6-di-(methylamino) s-triazine is employed.

Example 3 Diamino s-triazinyl para-hydroxytolyl-carbamyl-methyl sulfide is prepared in essentially the same manner as described under. Example 1 with the exception that, instead of para-(chloroacetamido) phenol, an equivalent amount of para-hydroxytolyl-carbamyl chloro methane is employed.

Example 4 Diamino s-triazinyl alphaor beta- (para-hydroxy-phenyl-carbamyl) ethyl sulfide is prepared in essentially the same manner as described under Example 1 with the exception that, instead of para-(chloroacetamido) phenol, an equivalent amount of alpha-(para hydroxyphenyl carbamyl) alphaor beta-chloro ethane is employed.

Example 5 This example illustrates the preparation of diamino s-triazinyl ortho-hydroxyphenyl-carbamyl-methyl sulfide.

' Parts Ortho-(chloroacetamido) phenol 185 Mercapto diamino s-triazine 143 Sodium hydroxide The mercapto diamino s-triazine was added to a solution of the sodium hydroxide dissolved in 300 parts water. The mixture was stirred until all the solid had dissolved. The solution was filtered. The ortho-(chloroacetamido) phenol was added to the filtered solution and the mixture was stirred to facilitate complete solution of the ortho-chloroacetamido phenol. An acid, specifically hydrochloric acid, was added to the reaction mass in an amount just suincient to make the solution neutral to litmus.

and thirty-eight (238) parts of aqueous hydro- .chloric acid containing approximately 38% HCl was suificient to neutralize the solution. This resulted in the precipitation of a solid comprising diamino s-triazinyl ortho-hydroxyphenyl-carbamyl-methyl sulfide. The precipitated solid was removed by filtration and washed until all soluble salts had been extracted. The residue was dried at 70 C. for several hours to obtain the purified diamino s-triazinyl ortho-hydroxyphenyl-carbamyi-methyl sulfide. The compound of this example, like the product of Example 1, lacked the vesicant characteristics of the ortho- (chloroacetamido) phenol from which it was prepared.

The diamino s-triazinyi ortho-hydroxyphenylcarbamyl-methyl sulfide can be obtained directly,

that is, without the acidification step, by using only sufiicient sodium hydroxide to form the sodium salt of the mercapto diamino s-triazine as an intermediate product.

Illustrative examples of other compounds of this invention, and which may be prepared as hereinbefore described, are:

Diamino s-triazinyl meta-hydroxyphenyl-carbamyl-methyi sulfide 4,6 di (methylamino) s-triaziny1-2 ortho-hydroxyphenyl-carbamyl-methyl sulfide 4,6 di (methylamino) s-trlazinyl-2 meta-hydroxyphenyi-carbamyl-methyl sulfide Diamino s-triazinyl ortho-hydroxyphenyl-thiocarbamyl-methyl sulfide Diamino s-triazinyl meta-hydroxyphenyl-thio carbamyl-methyl sulfide where n represents an integer and is at least 1 and not more than 2, Z represents a member of the class consisting of oxygen and sulfur, Y represents a divalent carbocyclic radical, and R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halohydrocarbon radicals.

5. Chemical compounds corresponding to the general formula IIIHR where Y represents a divalent carbocyclic radical, and R represents a member of the class consisting or hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals.

6. A diamino s-triazinyl hydroxycanbocycliccarbamyl-methyl sulfide.

7. A diamino s-triazinyl hydroxyphenyl-carbamyl-methyl sulfide.

11. The method of preparing chemical compounds corresponding to the general formula II ItHN-C fecting reaction, in the presence of a hydrohalide 8. Diamino s-triazinyl ortho-hydroxyphenylcarbamyl-methyl sulfide.

9. Diamino s-triazinyl para-hydroxyphenylcarbamyl-methyl sulfide.

10. A diamino s-triazinyl hydroxytolyl-carbamyl-methyl sulfide.

acceptor, between (1) a mercapto triazine corresponding to the general formula NHR where R has the meaning above given, and (2) a halide corresponding to the general formula xo..a,,.t iNa-r-on where X represents halogen, and n, Z, Y and B. have the meanings above given.

12. A method as in claim 11 wherein the hydrohalide acceptor is an alkali-metal hydroxide.

13. The method of preparing a diamino s-triazinyl hydroxyphenyl-carbamyl-methyl sulfide which comprises effecting reaction, in the presence of a hydrohalide acceptor, between thioammeline and a chloroacetamido phenol.

14. The method of preparing diamino s-triazinyl para-hydroxyphenyl-carbamyl-methyl sulfide which comprises effecting reaction, in the presence of an alkali-metal hydroxide, between thioammeline and para (chloroacetamido) phenol.

15. The method of preparing diamino s-triazinyl ortho hydroxyphenyl carbamyl methyl sulfide which comprises efiecting reaction, in the presence of an alkali-metal hydroxide, between thioammeline and ortho (chloroacetamido) phenol.

GAETANO F. DTALELIO. 

